Conversion of solid fuels and products derived therefrom or other materials into valuable liquids



C. KRAUCH ET AL Oct. 24, 1933.

CONVERSION OF SOLID FUELS AND PRODUCTS DERIVED THEREFROM OR OTHER MATERIALS INTO VALUABLE LIQUIDS Original Filed Feb. 6, 1926 INVENTORS Cavi KTQ-uch BY 77ZaL'aSPZ'er A ORNEYS Patented Oct. 24, 1933 UNITED STATES CONVERSION OF SOLID FUELS AND PROD- UCTS DERIVED THEREFROM OR OTHER MATERIALS INTO VALUABLE LIQUIDS Carl Krauch, Ludwigshafen-on-the-Rhine, and Mathias Pier, Heidelberg, Germany, assignors, by mesne assignments, to Standard-I. G. Com-l pany, Linden, N. J., a corporation ol' Delaware Original application February 6, 1926, Serial No. 86,646, and in Germany February 16, 1925. Divided and this application April 7, 1927.

Serial No. 181,884

25 Claims. (Cl. 196-53)` One of the most important and widely agitated problems in the industrial world has for a long time been how to produce good gasoline or other valuable liquid fuels from solid fuel including coal in all its varieties and wood, and

productsl of distillation or mineral oils especially heavy oils.

One attempt at the solution of this problem 4has been made by the so-called liquefaction of 0 coals by means of hydrogen or by destructive hydrogenation of tars or oils under a high pressure and at a high temperature but this has not reached application industriallybecause of an unsatisfactory speed and rate of the conversion.

By the process described in the specification of the original application No. 86,646 filed February 6th, 1926 of which this is a division, we claim to have successfully solved this problem for the first time and to be lable to produce good pure liquid fuels, including also benzines from solid fuels and to convert also tars obtained from solid fuels and also heavy mineral oils, or crude oils, or residues into more valuable liquid products, including benzines by a process economical in material, time, labour and wear of the apparatus.

In arriving at this result we have made sev- 30 eral discoveries or inventions to certain of which this application is directed.

We conceived the idea of applying a catalyst to the said solid fuel or other materials, in connection with said hydrogenizing high pressure and high temperature process, but found that an improvement of the process could not be obtained at all or at least not in a continuous operation. Thereafter We discovered that the cause of this drawback was the sulfur present in the treated material and We found that an addition of inorganic compounds of nitrogen to the materials which are to be brought into reaction has a very good catalytical effect notwithstanding the presence of sulfur or sulfur compounds.

As examples of inorganic nitrogen compounds to be added, we mention ammonia, or ammonium sulfid, or nitrides, for example silicon or titanium nitrides. Several compounds of nitrogen of different character, for example solid and gaseous compounds as nitrides and ammonia may be used at the same time. Instead of nitrogen compounds, free Anitrogen may be added to the hydrogen gas in the presence or with an 55 addition of contact masses capable of synthesizing ammonia, but in such cases ammonia or other compounds of nitrogen may also be added simultaneously. Hereinafter in the specification and claims when we refer to the process. being carried out in the presence of an inorganic nitrogen compound, we contemplate both the addition of inorganic nitrogen compounds as such and the addition of substances which give rise to inorganic nitrogen compounds under the conditions of Working, for example, the addition of substances giving rise to the formation of ammonia, such as nitrogen. The amount of catalyst used with reference to the amount of material 'to be converted may range within very wide limits. The proper amount will de-` pend upon the other factors of the process, such as, the size ofthe reaction vessel, the size of the charge, the facilities for bringing the charge into contact with the catalyst, the temperature, the pressure and the density of the charge in each particular instance. A certain amount of experimentation will be necessaryA to determine the minimum amount of catalyst which can be used, but amounts which are many times larger" than those usually employed may also be used without impairing the quality of the final product and Without giving rise to any other inconvenience. Since the catalysts act by contactfwith the treated materials the amount of the catalyst required for effecting a satisfactory speed of the reaction depends also onl the state of motion in which the treated materials are kept. For example, in the case of rigidly arranged solid catalysts the amount thereof required is smaller when the materials treated are kept in motion by stirrers or other moving devices than when they are moved on merely by the flow maintained in a continuous operation. The catalysts may be added in an amount of the order of about one tenth of the amount of treated materials present, it being understood that the same amount of catalyst may be used for long periods for converting further amounts of initial materials.

The catalysts employed according to the pres- 100 ent invention may be added in any suitable manner. They may be added to the solid or liquid material, or in the case of liquids they may be introduced into the reaction vessel and the liquids brought into contact With them in 105 a vaporized or otherwise finely divided state. Other bodies, for example, lumps of brick, quartz, asbestos, coke, active carbon, silica gel, metals, especially heavy metals, or metal oxids, 0r carbids, or mixtures of such bodies which 4pressure hydrogenation of solid or liquid fuels,

or components or conversion products of all above mentioned materials, such as cracked products, cumaron'e or 'any other resins or residues of their distillatio.- pitch, asphalt and 'so on, or mixtures of several such products with each. other, also of solids with liquids or of one or more oi such products with other suitable organic liquids. v

Especially when employing coal or liquid fuels, an addition of lignite or peat is often of advantage, oten increasing the hydrogenating action, avoiding several drawbacks and in the case of solid substances rendering their introduction easier.

All the said materials may be used in the presence of substantial amounts of water and, if desired, water may be added as such. Sometimes the process of hydrogenation is hereby iurthered. For example, lignite producer tar containing from d0 to 50 per cent of water may be used to advantage directly.

The preferred form of carrying out the process is generally a continuous operation with a stream of the gases and with an excess -'thereof over the required quantity and preferably while I maintaining the desired pressure by adding fresh gas and passing the gas either by circulation through one or more reaction vessels or through a succession of several reaction vessels. The material to be converted is supplied A at a proper place and the products are separated from' the reaction gases by cooling.

The gases serving for the reaction may consist of hydrogen alone or of mixtures containing hydrogen, for example a mixture of hydrogen with nitrogen, or water gas, or hydrogen mixed with. carbon dioxid, hydrogen sulphide, water vapor or methane or other hydrocarbons. Or the hydrogen may be generated in the reaction chamber by the interaction of -water and carbon monoxid, and the like. When employing nitrogen compounds as catalysts, and carbon'monoxid and water the gas must be employed in a stream.

'l'lhe hydrogen is supplied to the materials to be treated in substantial amounts. When working in the gaseous phase the amount of hydrogen is, as a rule, so selected that its volume occupies about from 50 to 90 per cent of the total volume of the reactants. When working in the liquid phase a corresponding amount of hydrogen with reference to the materials to be converted is employed. Generally, it may be said that the rate of flow of hydrogen is in excess of 'about Seil liters per kilogram of carbonaceous material.

The process is best carried out under elevated or 'even strongly elevated pressure and most suitably witha stream of the gas passed through or over the material to be treated or carrying it along. the reaction vessel by which.

method the production obtained .by the process is very large. l

Depending on the conditions of working, for example temperature and pressure employed or duration of the treatment, the products are poor or rich in products of low boiling point. Generally the temperature ranges betweenl 300 and '700 degrees centigrade, and when working under pressure, it should amount to 20, 50 or more atmospheres.

Compounds obtained by the aforedescribed hydrogenation treatment of solid fuels, tars, mineral oils and other materials referred`A to, which compounds may be comprised by the term destructively hydrogenized fuels/are generally very low in sulfur or even completely free therefrom and are excellently suitable for use as fuel for internal combustion engines, as far as the low boiling portions are concerned. Fractions of higher boiling point may also be obtained which may be used as lubricants.

The process according to the present invention will be further illustrated with reference.l

to the accompanying drawing which shows in vertical cross section an apparatus for carrying out the said process. It should be understood that the invention is not limited to the apparatus illustrated in the said drawing.

A is a pump for the introduction of solid materials, B is a heating coil, E is a reaction vessel, C is a vessel for heating the hydrogenating gas and is tted with an electric heater D. F and H are separating vessels.

Finely ground Esthonan oil shale mixed with 10 percent of chromium nitride is pressed through theheating coil B, in which it is heated ico lill@ lll@ to a temperature of about 350 C. and through I the pipe M into a reaction vessel E by means of a pump A actuated under a pressure of 200 atmospheres. Hydrogen having a pressure of about 200 atmospheres is introduced through the pipe U, and after being mixed with the proper amount of ammonia supplied by pipe Y, is passed into the preheating vessel C fitted with the electric heating device D and is therein preheated to a temperature of between about 550 and 600 C. In this manner a temperature of about 460 C. isset up in the reaction vessel. 'Ihe reaction products then pass on through the pipe N into the separating vessel F in which a constant level of liquid is maintained by constant removal of the unimproved constituents of the shale through the pipe S and the cooler K. The gaseous and vaporous products leave the separator F at P and are condensed in the condenser G. The mixture of gases and liquid is introduced at Q into the separator H, the liquid products being removed by way of the pipe T through the cooler L. The hydrogenating gases leave the separator at R and may be returned to the process, if desired after a purication treatment, by Way of the pipe J purifier W filled With any suitable absorbing material, `and circulating pump X. The liquid reaction products contain 80 percent of the carbon which was originally present in the form of organic compounds in the oil shale as valuable middle oils. The said middle oils may be converted into a valuable motor fuel by a further destructive hydrogenation process.

The followng'examples will serve to further explain how our invention is carried out in practice, but we do not restrict our invention to these examples.

Aricamare 1 mospheres, after an addition has been made to the gas of 1 per cent, by Volume, of ammonia. The products of the reaction are carried away with the gas current and condensed by cooling 'after leaving the furnace, whereby a thin oil with but little phenolic bodies is obtained. At length per cent or more of the carbonaceous matter contained in the brown coal is liquefied and at the same time 10 per cent of gaseous hydrocarbons are formed.

The conditions of working may be varied to a large extent; the pressure may be lower or higher. In addition to ammonia other catalysts, or solid bodies may be employed, for example, iron, cobalt, or the like, or porous lumps of clay, which materials may be added to thecoal, or added separately. The brown coal may be mixed with a liquid, for example part of the product obtained as described.

Example 2 A vessel suitable to withstand high pressure is supplied with pieces of pressed aluminium hydroxid and heated to about 500 C. and a gas mixture composed of 79 per cent, by volume, of hydrogen, 20 per cent of nitrogen and 1 per cent of ammonia, charged with the vapors of dehydrated brown coal producer tar at a low partial pressure is led through under a pressure of 200 atmospheres. On cooling the gases leaving the vessel, a product containing thin liquid hydrocarbcns is obtained, which is practically free from oxygenated and unsaturated compounds. The residual gas mixture may be returned to the reaction vessel after replacing the consumed hydrogen and removing gaseous hydrocarbons which are formed to a small extent.

When employing titanium nitrid instead of ammonia and aluminium hydroxid, and the above gas mixture or hydrogen alone under similiar conditions, a product containing about 70 per cent its weight of gasoline boiling up to 200 C. is obtained.

Mixtures of coals and tars or of coal or tar with products of the hydrogenation of such materials or with other suitable liquid diluents may also be employed.

Example 3 Dark-colored residues of an American rock oil, which at ordinary temperature are nearly solid and have a strongly unsaturated character, are incorporated with an excess of a gas mixture composed of 3 parts, by volume, of hydrogen and 1 part of nitrogen, with or without an addition of free ammonia, and passed in a continuous manner over an activated iron catalyst as suggested for the synthesis of ammonia, at a pressure of 200 atmospheres and a temperature of from 450 to 500 C. The product which is formed besides a little methane is a slightly yellowish liquid of 0.800 or less sp. gr. which on distillation yields about 50 per cent petrol boiling up to 150 C. of saturated character, up to 250 C. additional 28 per cent distillate and leaves at 325 C. about 5 per cent of a thick or vaseline-like weakly colored residue.

With silicon or titanium nitrid instead of activated iron and the above gas mixtureor pure hydrogen a similar result is obtained.

In all of the above examples, the hot parts of the apparatus may be lined or coated with aluminium or aluminium alloys or chromium or made of or coated with an alloy of 60 per cent of nickel, 27.7 per cent of iron, 12 per cent of chromium and 0.3 per cent of carbon; or an alloy composed of 58 per cent of nickel, 25 per cent of iron, 17 per cent of chromium and 0.03 per cent of carbon; or an alloy composed of 96 per cent of iron, 1.75 per cent of nickel, 1.5 per cent of chromium, 0.1 per cent of carbon and also of 0.25 per cent of silicon, 0.27 per cent of manganese, besides small quantities of copper, sulfur and phosphorus.

Our invention is not conned to the above examples; the conditions may be widely varied in various directions. For example the pressures and temperatures may be higher or lower than stated above.

In the appended claims, the expression distillation and extraction products thereof is intended to relate only to solid and liquid distillation and extraction products and is not to be construed to include normally gaseous products of the distillation of solid and liquid fuels.

Also, when the catalyst set forth in the claims is defined as being added, it is not to be construed as necessarily meaning that the catalyst is introduced into the reaction chamber with each charge of carbonaceous material, but is to be construed to mean that the reaction is carried out in the presence of an effective quantity of a catalytic material which is not naturally contained in the carbonaceous material undergoing treatment or is contained in said carbonaceous material infineffective quantities.

What we claim is:

1. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, which comprises treating them with an excess of added free hydrogen in the presence of an inorganic nitrogen compound as a catalyst and heat at a temperature suil'lcient `to promote th'e conversion and at a pressure of at least 20 atmospheres.

2. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof which comprises treating them with an excess of added free hydrogen in the presence of an added inorganic nitrogen compound as a catalyst and heat at a temperature suflicient to promote the conversion and at a pressure of at least 20 atmospheres, the conditions of working, such as temperature, pressure and the efficiency of the catalyst, being so adapted to each other as to give rise to the formation of substantial amounts of low, boiling hydrocarbons of a benzine character.

3. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof which comprises treating them with a stream of an excess of free added hydrogen in the presence of an added inorganic nitrogen compound as a catalyst and heat at a temperature sufficient to promote the conversion and at a pressure of at least 20 atmospheres.

4. The process of converting carbonaceous substances, such as solid and liquid fuels, dised to each other as to give rise to the formation of substantial amounts of low boiling hydrocarbons of a gasoline character.

5. The process of converting carbonaceous substances, 'such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with an excess of added free hydrogen and more than one added inorganic nitrogen compound as catalysts and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 20 atmospheres.

6. The process of converting carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with an excess of added free hydrogen and an added inorganic nitrogen compound as a catalyst, in the presence of a substantial amount of water, and heat at a temperature of between about 300 and 700 C. and at a pressure of at least 50 atmospheres.

7. The process of producing liquids from solid fuel materials which comprises destructively hydrogenating said materials with an excess of added free hydrogen in the presence of an added inorganic nitrogen compound at a pressure upwards of 100 atmospheres and at a temperature of ltween about 300 and 700 C.

8. The process of producing liquid hydrocarbons from lignite which comprises destructively hydrogenating the initial material lignite with an excess of added free hydrogen in the presence of an added inorganic nitrogen compound at a pressure of at least 20 atmospheres and at a temperature of between about 300 and 700 C.

9. The process of converting carbonaceous substances, such as solid and vliquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating a mixture of one of said substances with a substance of the nature of lignite or peat by destructive hydrogenation with an excess of added free hydrogen in the presence of an added inorganic nitrogen compound as a catalyst under a pressure of at least 20 atmospheres and at a temperature of between about 300 and 700 C.

l0. The process of destructively hydrogenizing carbonaceous substances, such as solid and liquid fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them with an excess of added free hydrogen in the presence of an added inorganic nitrogen compound/as a catalyst at a temperature sufficiently high for the conversion and at a pressure of at least 20 atmospheres for a period such that, under the conditions as above given, the product is substantially free from asphalt.

11. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature such as between about 300 and 700 C. at a pressure of at least 20 atmospheres with an excess of added free hydrogen in rasata@ the presence of an 'added inorganic nitrogen compound as a catalyst.

12. The process-of converting solid and liquid carbonaceous 'materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated 'temperature such as between .about 300 and 700 C. at a pressure of upwards of 100 atmospheres with an excess of addedfree hydrogen in the presence of an added inorganic nitrogen compound as a catalyst.

13. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and` extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature such as between about 300 and 700 C. at a pressure of at least 20 atmospheres with an excess of added free hydrogen in the presence of added ammonia as a catalyst.

14. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature such as between about 300 and 700 C. at a pressure of upwards of 100 atmospheres with an excess of added free hydrogen in the presence of added ammonia as a catapheres with a stream of an excess of free added hydrogen in the presence of an addedinorganic nitrogen compound as a catalyst. I

16. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature such as between about 300 and 700 C. at a pressure of upwards of 100 atmospheres with a stream of an excess of free added hydrogen in the presence of an added inorganic nitrogen compound as a catalyst.

v17. The process of converting solid and liquid carbonaceous material such as fuels, distillation and extraction products thereof, into valuable liquids substantially free from asphalt which comprises treating them with an excess of added free hydrogen at an elevated temperature such as between about 300 and 700 C. in the presence of an added inorganic nitrogen compound as a catalyst at a pressure of at least 20 atmospheres, the initial materials and the hydrogen being continuously introduced to the reaction vessel and the reaction-products being continuously removed therefrom.

18. The process of converting solid and liquid carbonaceous material such as fuels, distillation and extraction products thereof into valuable liquids substantially free from asphalt which comprises treating them with a stream of an excess of free added hydrogen at an elevated temperature such as between about 300 and 700v C. in the presence of an added inorganic nitrogen compound as a catalyst and at a pressure of at least 20 atmospheres, and removing the product from the reaction chamber in admixture with the stream of escaping hydrogen.

19.' The process of converting solid and liquid carbonaceous material such as fuels, distillation and extraction products thereof into valuable liquids substantially free from asphalt which comprises treating them with a stream of an excess of free added hydrogen atan elevated temperature such as between about 300 and 700 C. in the presence of an added inorganic nitrogen compound as a catalyst and at a pressure of at least 20 atmospheres, removing the product from the reaction chamber in admixture with the stream of escaping hydrogen, separating the reaction productfrom the admixed hydrogen, and returning the hydrogen to the reaction zone.

20. The process of converting solid and liquid carbonaceous material such as fuels, distillation and extraction products thereof, into valuable liquids substantially free from asphalt, which comprises treating them at an elevated temperature, such as between about 300 and r100 C. and at a pressure of at least 20 atmospheres with hydrogen and an addition of ammonia as a catalyst, the initial materials and the hydrogen being continuously introduced to the reaction vessel and the reaction products being continuously removed therefrom.

21. The process of converting solid and liquid carbonaceous material such as fuels, distillation and extraction products thereof, into valuable liquids substantially free from asphalt, which comprises treating them at an elevatedtemperature, such as between about 300 and '700 C. and at a pressure of at least 20 atmospheres with a stream of an excess of free added hydrogen and an addition of ammonia as a catalyst and removing the product from the reaction chamber in admixture with the stream of escaping hydrogen. I

22. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevatedl temperature, such as between about 300 and 700 C. at a pressure of at least 20 atmospheres with a stream of an excess of free. added hydrogen and an addition of nitrogen and a contact mass which aids the synthesis of ammonja, the synthesized ammonia acting as a catalyst.

23. The process of converting solid and liquid carbonaceous substances such as uels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature, such as between about 300 and 700 C. at a pressure upwards of 100 atmospheres with a stream of an excess of free added hydogen and an addition of nitrogen and a contact mass which aids the synthesis of ammonia, the synthesized ammonia acting as a catalyst.

24. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature, such as between about 300 and 700 C. at a pressure of at least 20 atmospheres with an excess of added free hydrogen in the presence of added titanium nitride as a catalyst.

25. The process of converting solid and liquid carbonaceous materials such as fuels, distillation and extraction products thereof, into valuable liquids which comprises treating them at an elevated temperature, such as between about 300 and 700 C. at a pressure of at least 20 atmospheres with an excess of added free hydrogen in the presence of added silicon nitride as a catalyst.

" CARL KRAUCH.

MATHIAS PIER.

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Acting Commissioner ed Pmeme. 

